Organic peroxides derived from unsaturated compounds

ABSTRACT

New organic peroxides having the formula   are prepared by reacting a monohydroperoxide of the formula R5OOH or R6OOH with an unsaturated carbonyl compound having the formula   the reaction being carried out in the presence of an acid catalyst at a temperature between about -30*C and +80*C, the molar ratio of the carbonyl compound to the hydroperoxide being between about 1:2 and 1:10. The new organic peroxides are particularly useful for crosslinking plastomers, vulcanizing elastomers, and as initiators for radical polymerizations.

United States Patent [191 Sacrini et a1.

1 1 ORGANIC PEROXIDES DERIVED FROM UNSATURATED COMPOUNDS [75] Inventors: Egeo Sacrini; Claudio Cavallotti,

both of Milan, Italy [73] Assignee: The BF Goodrich Company, Akron,

Ohio

[22] Filed: July 8, 1970 [21] Appl. No: 53,267

[30] Foreign Application Priority Data Apr. 11, 1970 Italy e. 20222/69 [52] US. Cl 260/6l0 R; 260/41; 260/783;

260/784; 260/239; 260/803 [51] Int. Cl. C071: 73/00 [58] Field of Search 260/610 R [56] References Cited UNITED STATES PATENTS 12/1948 Dickey 260/610 R 2,490.282 12/1949 Seubold 260/610 R 3,296,184 1/1967 Porlolani et al. 260/610 R FOREIGN PATENTS OR APPLICATIONS 1,043.571 9/1966 United Kingdom 260/610 R 1451 July 22, 1975 Primary Examiner-Bernard Helfin Assistant Examiner-W. 8. Lone Attorney. Agent, or Firm-Hubbell, Cohen and Stiefel [57] ABSTRACT New organic peroxides having the formula 12 la 1C are prepared by reacting a monohydroperoxide of the formula R OOH or R OOH with an unsaturated carbonyl compound having the formula 8 Claims, No Drawings 1 ORGANIC PEROXIDES DERIVED FROM UNSATURATED COMPOUNDS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to new organic peroxides and more particularly to new organic peroxides which have a double peroxidic function and are derived from unsaturated compounds. as well as to the use of these new organic peroxides in the crosslinking of plastomers, the vulcanization of elastomers and as organic reactants.

2. Description of the Prior Art Organic peroxides are used as initiators for radical polymerization, vulcanizing agents for elastomers, and cross-linking agents for thermoplastic polymers. A discussion of typical organic peroxides used in the prior art, their preparation, and some difficulties associated with the preparation and use of some prior art peroxides appears in US. Pat. No. 3,489,730, which was issued on Jan. 13, 1970, and the contents of which are hereby incorporated herein by reference.

The present invention provides a particular class of new organic peroxides having good stability and low volatility, which peroxides are particularly suited and interesting both as cross-linking agents for plastomers and as vulcanizing agents for elastomers.

SUMMARY OF THE INVENTION The present invention provides a new series of peroxides with a double peroxidic function characterized by one or more unsaturated bonds and having the general formula:

cos, it 0012.

wherein R, is selected from the group consisting of unsubstituted, alkyl substituted and halogen substituted cycloalkyl radicals having -30 carbon atoms; unsubstituted, alkyl substituted, hydroxy substituted and halogen substituted phenyl radicals having 6-26 carbon atoms; and unsubstituted, alkyl substituted and halogen substituted heterocyclic radicals having 4-l5 carbon atoms; R, is selected from the group consisting of hydrogen, alkyl radicals having l-l2 carbon atoms, unsubstituted, alkyl substituted and halogen substituted cycloalkyl radicals having 5-20 carbon atoms, halogen substituted alkyl radicals having l-l2 carbon atoms; and unsubstituted, alkyl substituted and halogen substituted phenyl radicals; and R, and R, together with the carbon atom to which they are bonded may form a cycloaliphatic ring selected from the group consisting of unsubstituted and alkyl, phenyl, phenylalkyl, alkylidene and phenylalkylidene substituted cyloaliphatic rings having 5-30 carbon atoms; R; and R are each selected from the group consisting of hydrogen, alkyl radicals having l-l2 carbon atoms, unsubstituted, alkyl substituted and halogen substituted cycloalkyl radicals having 5-20 carbon atoms; unsubstituted, alkyl substituted and halogen substituted phenyl radicals having 6-20 carbon atoms; halogen substituted alkyl radicals having l-l2 carbon atoms, and halogen substituted phenylalkyl radicals having 7-20 carbon atoms; and R and R, taken together with the two adjacent carbon 7 atoms to which they are respectively bonded may form a cycloaliphatic ring selected from the group consisting of unsubstituted and alkyl, phenyl, phenylalkyl, alkylidene, phenylalkylidene and hydroxyphenylalkylidene substituted cycloaliphatic rings having S-25 carbon atoms; R,, and R are each selected from the group consisting of alkyl radicals having 4-12 carbon atoms, phenylalkyl radicals having 9-18 carbon atoms, unsubstituted, alkyl substituted and halogen substituted cycloalkyl radicals having S-2l carbon atoms; unsubstituted, alkyl substituted and halogen substituted phenylcycloalkyl radicals having 9-25 carbon atoms; halogen substituted alkyl radicals having 4-l2 carbon atoms, and halogen substituted phenylalkyl radicals having 9-18 carbon atoms.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Tertiary alkyl groups, for example, tert-butyl, tertamyl and cumyl, are preferred as the R and R radicals.

Examples of compounds of the present invention within the above general formula, include:

. l-phenyl-3,3-di( tert-butyl-peroxy )-propene-l;

. l-phenyl-3,3-di(cumyl-peroxy)-propene-l;

. l -phenyl-3,3-di(tert-butyl-peroxy)-butenel l -phenyl-3,3-di(cumyl-peroxy )-butene-l l-phenyl-3-tert-butyl-peroxy-3-cumyl-peroxybutene-l;

f. l-cyclohexylidene-2,2-di(tert-butyl-peroxy ethane;

g. l-furyl-3 ,3-di(tert-butyl-per0xy )-propene-l h. l-furyl-2-methyl-3,3-di( tert-butyl-peroxy propene-l;

i. 1,l -di(tert-butyl-peroxy )-2-benzylidenecyclohexane;

l. l, l -di(tert-butyl-peroxy )-2,6-di( 4-hydroxy-benzylidene)cyclohexane; and

m. 1, l -di(tert-butyl-peroxy)-2,6-di(4-isopropyl-benzylidene)cyclohexane;

n. l-cyclohexyl-3,3-di(tert-butyl-peroxy)-butene-l;

o. 2,3-di(phenyl)-4-di(tert-butyl-peroxy)-butene-2;

p. l-phenyl-3 ,3-di( cyclohexen-2-yll -peroxy)propene-l;

l -phenyl-3,3-di(cyclohexen-2-yll -ethyl-peroxy propenel;

r. l-phenyl-3,3-di(tetralinl -peroxy)propene-l;

s. l-phenyl-3,3-di(tetralin-l-methyl-1-peroxy)propene-l.

The diperoxides of this invention have the unusual properties of having good stability and low volatility at temperatures above room temperature. These properties permit the compounds to be incorporated in plastomers as crosslinking agents and in saturated elastomers as vulcanizing agents without giving rise to the troublesome secondary phenomena (for instance prevulcanization and pre-crosslinking) which arise when using less stable, more volatile, prior art peroxides.

In accordance with a preferred embodiment, the diperoxides of the invention may be prepared by reacting an unsaturated carbonyl derivative, dissolved in a suitable solvent, with an organic hydroperoxide in the presence of an acid catalyst at a temperature between about 30 and +C, preferably between about l 0 and +50C.

The unsaturated carbonyl compounds which may be used in the foregoing reaction have the general formula pane-m wherein R R R and R, are as defined above. Examples of such carbonyl compounds include, for instance, cinnamic aldehyde. furyl-acrylic aldehyde, alphacyclo-hexylidene-acetaldehyde, alpha-benzylideneacetone and 2,6 benzylidene-cyclohexanone.

The hydroperoxides which may be used in the reaction have the general formula ROOH wherein R represents R and R as defined above. Examples of such compounds include: tert-butyl hydroperoxide, and sub stituted derivatives thereof; cumyl-hydroperoxide and substituted derivatives thereof; 1,3 diisopropylbenzene-a-monohydroperoxide and 1,4 diisopropylbenzenea-monohydroperoxide; l-methyl-cyclohexylhydroperoxide; 2-methyl-2-hydroperoxy-butyn3; lmenthane-hydroperoxide; and l-phenyl-cyclohexyl hydroperoxide.

The solvents which may be employed in the reaction include for example, linear aliphatic hydrocarbons having 6 to 10 carbon atoms, linear aliphatic halogenated hydrocarbons having 1 or 2 carbon atoms and from 1 to 4 chlorine atoms, aromatic hydrocarbons, having from 6 to 9 carbon atoms, which may be halogenated with l or 2 chlorine atoms, cycloaliphatic hydrocarbons having 6 to 10 carbon atoms, and ethers, such as ethylether.

The molar ratio of unsaturated carbonyl compound to hydroperoxide is between about 1:2 and 1:10, perferably between about 1:25 and 1:5.

The catalysts used are preferably sulfonic acids, such as for instance, para-toluene sulphonic acid.

The new diperoxides of the present invention are soluble in chlorinated and unchlorinated aliphatic and aromatic hydrocarbon solvents, and in aliphatic esters. A particular feature of this invention is that the diperoxides of the invention are excellent crosslinking agents for plastomers, vulcanizing agents for elastomers and initiators for radical polymerizations. The use of the diperoxides defined above for the crosslinking of plastomers is particularly applicable to polyolefins and more particularly to polyethylene.

The crosslinking of polyethylene with the peroxides of the present invention results in a product having improved mechanical propcrties at high temperatures, reduced fragility at low temperatures and reduced solubility in aliphatic and aromatic hydrocarbons, even chlorinated ones. Furthermore. the crosslinked polyethylene has increased resistance to light, weather and to ageing.

The crosslinking is carried out in accordance with this aspect of the invention at a temperature between about 100 and 200C, preferably between about 145 and 165C, at a pressure between about 50 and 200 lcg/cm and for periods of from about to 60 minutes, preferably from about to 30 minutes. The concentration of the peroxide is between about 0.5 and 10% by weight, preferably between about 2 and 5% by weight, based on the weight of the plastomer.

The vulcanization of elastomers, for example, ethylene/propylene copolymers, in accordance with the present invention may be carried out at a temperature between about 140 and 190C. preferably between about 150 and 170C, for periods of from about 5 to 200 minutes, preferably between about 5 to 15 minutes. The concentration of the peroxide is between about 0.5 and 10% by weight, preferably between about 2 and 5% by weight, based on the weight of the elastomer.

Particularly suitable vulcanization mixes for vulcanizing ethylene/propylene copolymer have compositions within the following ranges:

ethylene/propylene copolymer 100 pts. by wt. carbon black 20 to pts. by wt. ZnO l to 10 pts. by wt. sulfur 0.15 to 05 pt. by wt. peroxide 0.005 to 0.02 mole The most notable advantages afforded by the use of the diperoxides of the present invention in the crosslinking of plastomers and in the vulcanization of saturated elastomers include: practically odorless crosslinked and vulcanized products; absence of blooming" phenomena; short vulcanization times and low vulcanization temperatures; the greater effectiveness of the new diperoxides remains unaltered even in the presence of known fillers, reinforcing agents (for instance carbon black, Mg hydrosilicate), additives of the type ageing resistant plastified and homogenized masses can be obtained without pre-crosslinking or prewulcanization phenomena which hinder further processing.

The possibility of obtaining plastified and homogenized masses without pre-crosslinking or pre-vulcanization phenomena is due to the fact that the peroxides do not thermally decompose to the mixing temperature giving rise to the beginning of the pre-crosslinking and pre-vulcanization phenomena.

The following examples are presented to further illustrate the present invention.

EXAMPLE 1 200 g of anhydrous benzene and 131.5 g of 80% tertbutyl hydroperoxide were introduced into a flask at ambient temperature provided with a stirrer. The temperature was then increased to 40C and, during 10 minutes, there were simultaneously added 51.6 g of 98% cinnamic aldehyde and 100 g of a benzene/methanol solution of paratoluensulfonic acid, having the following composition by weight:

0.14% of paratoluenesulfonic acid, 1,42% of anhy drous methanol, and 98.44% of anhydrous benzene.

The mixture was then stirred for 3 hours at 40C. Thereafter, the organic solution was washed with an 8% aqueous solution of NaHCO then with 5% aqueous NaOH, and finally with water to a pH of 6.5.

The solvent was then removed under vacuum (final pressure, 0.2 mm Hg) at 30C, obtaining 92 g ofa white crystalline product as residue.

After repeated recrystallizations from methanol, there were obtained 75 g of a solid crystalline product which was identified as 1-phenyl-3,3-di(tert-butylperoxy)-propene-l. This product had the following characteristics:

melting point: 58-S9C iodometric titer: 98% decomposition temperature: 1 18C half life at C: 30 minutes carbon content. weight found: 69.0

' t-Continuecl r carbon content. weight calculated: 69.36 hydrogen content, weight 1! found: 9.1

hydrogen content, weight calculated:

6 0.2%01' paratoluenesultonib acid. 1.4% of absolute v ethyl alcohol and 98.4% of benzene. This mixture was then stirred for 3 hours at 45C, and at the end of this time it was washed with water, then .with a 5% NaHCO solution, then with 5% NaOH. and EXAMPLE finally with water until a neutral pH was reached. The 200 g of n-hexane and 120 g 59.0% tert-butyl hydrosolvent was then distilled under vacuum at 30 to 32C, peroxide were introduced into a flask at ambient temthereby obtaining 14 g of an oily yellow product identiperature provided with a stirrer. The temperature was tied as l-phenyl-3,3-di( y -p r y)-pr0pene-l. his increased to 42 to 45C and, during minute there l 0 product showed the following characteristics: were simultaneously introduced 48.8 g of distilled furyl-acrylic aldehyde and 161) got a benzene/methanol solution of paratoluenesulfonicacid having the follow- 1333 ing composition by weight: decompositiontemperature: 125C 1.42% of anhydrous methanol, 98.44%of anhydrous l5 jlggf g l 'fffl f d- 8 2 benzene and 0.14% of paratoluenesulfonic acid, carbon content: weight t calculated: 77:40! gag:sggiwmposmonasthesowfibnemployed 1113:2522 zzazntzzzszt:.r:.:1;...d. 31332. n x m This mixture was then stirred for 3 hours and 30 min- EXAMPLE 4 utes at a temperature of 42 to 45C. The organic solution was then washed with water, with an 8% NaHCO vulcamzatlon solution and then again with water to a PH of 6.5 The The vulcanization tests were CfllllEid OLlt on mixes of solvent was removed under vacuum at 40C. with a ethylene/Propylene copolyme. havmg a molar ratio final' pressure of 02 mmHg t ethylene/propylene 50/50 and a viscosity Mooney The solid residue l 19 g) was crystallized from meth- ML(1+4) C=35' In 1 there f Compared am) and there were thus obtained 101 g of a light yak the vulcanization rate s determmedon equtvalent mixes low crystalline product which was identified as l-furylf as pemXdeS respesnvelyv f 33 d-luert buty| per0xy pmpne 1' di(tert-butyl-peroxy)-propene-1; 1-furyl-3.3-dt( tert- The product had the following characteristics: bmylperoxylfpmpenel and l Peroxide i y The vulcanization rate was determined at 177C on a Monsanto TM-lO rheometer. The mixes used had the melting point: 56-57C -l composition: iodometric titer: 99.5% i decomposition temperature: 104C l V half life at l 18C: 30 minutes ethylene/propylene copolymer 100 pts. by wt. carbon content, weight found: 64.0% carbon black pts. by wt. carbon content, weight calculated: 63.36% ZnO 3 pts. by wt. hydrogen content, weight found: 8.7% sulfur 032 pt. by wt. hydrogen content, weight calculated: 8.51%. y peroxide Wu Q01 l i TABLE 1 vulcanization rate Parts per g of ethyvulcanization vulcanization Peroxide w temperature time g l C minutes ooc(cH,), CH==CHCH \OOIXCHU 2.94 O.Ql J 177 6 I CH OOC(CH -|)3 =CH-CH OocxCHalh P 2.84 0.01 177 5 o Dicumylperoxide 2.70 0.01 177 [4 EXAMPLE 3 50 cc of benzene and 14.5 g of 83.8% cumene hydro- 6O peroxide were introduced into a flask at ambient temperature provided with a stirrer. The temperature of the solution was thenincreased to 42 to 45C. Then, during 15 minutes, there were simultaneously added, dropwise, a mixture consisting of 5.1 g of 98.2% cinnamic aldehyde and 20 g of asolution of panatoluenesulfonic acid having the following composition by weight: r 1

peroxide).

a: From the results set forth in Table 2 it is clear that the peroxides of. the present invention permit the use of a low vulcanization temperature while. affording high vul- 3,896,176 7 8 canization rates and better physical characteristics of carried out at 80C for 21 hours. The degree of swelling the vulcanized product than those obtained by using is given by the following formula:

dicumylperoxide at higher temperature l65C) for (a h] longer periods of time (30 minutes). 1' I TABLE 2 Vuleanization Physical Properties of the Vulcanized Products Parts per l parts Tensile Elonga- Modulus Modulus Modulus of ethylene! Temp- Time strength tion at at at at Peroxide propylene eraminbreak I00% 200% 300% RHD copolymer lure ules kglcm it Elonga- Elonga- Elongaband "C tion tion tion ness mole g. kglcm' ltg/cm ltg/cm OOC(CH;) 0.0l5 4.4l 150 S 2l5 550 43 92 63 CH=CHCH l0 2l8 460 66 I27 65 OOC(CH I5 I92 370 24 67 I37 65 30 208 400 25 71 I38 65 60 I92 400 25 65 I33 65-66 I I OOC(CH;;l;| 0.010 3.4l I 5 I34 350 26 I06 66 CH=CH-CH 10 I45 390 27 60 I04 66 c OOCKH M I5 I49 400 25 57 102 66 30 I25 320 25 59 I06 66 60 I36 360 25 62 I09 65 V Dicumylperoxide 0.0m 2.70 I65 30 I 410 2| 5a 119 68 EXAMPLE 5 30 wherein a== weight of the test sample after 2l hours at C mslinkin 80C in xylene, b= weight of test sample before the test, r g r= weight of test sample after drying at the end of the The crosslinking tests were carried out on mixes of low-density (0.9l8) polyethylene and peroxide. Table 3 sets forth the physical properties of the polyethylene crosslinked by using, respectively, the diperoxides pre- 35 dam" of 1 cm we at 80C test.

pared in Example I l-phenyl-Il,3'di( tert-butyl-peroxdensity f xylene y)-propene-l Example 2 l-furyl-3.3-di(tert-butylp y -p p l and a know" F' (dlcu' Variations can, of course, be made without departing mylperoxide). from the spirit and scope of the invention.

The results thus Obtain d Show the emfellem. cross 40 Having thus described our invention, what we desire linking activity of the diperoxides of the invention. to secure b L patent and hereby claim TABLE 3 Moles of Crosslinking Physical Characteristics Peroxide peroxide Temp- Elonga- Degree of swellin g era- Yield Tensile tion at in in xylol at of Time ture point strength break 80 for 2l hours polyethylene minutes C kglcm kg/cm' in None 20 I45 57.8 73 I50 soluble /OOC(CH:!)3 C.H,-CH=CH-CH 0.0l 20 I45 52 I50 240 [0,4

()OCtC H 3 in l l CH=CH CH/OOC(CH:I): \OOCCHM 0.01 20 145 57 400 I4 Dicumylpcroxide 0.0l 20 I45 52.9 132 456 21.3

The determination of the degree of swelling was car- 60 I. An organic peroxide having the formula: ried out on the crosslinked product. By the term de' gree of swelling is meant the volume of solvent ab- OOR,-, sorbed by a given volume of crosslinked polyethylene. C The test method consists of suspending a small basket R, R, containing a plate of about 0.2 g ofcrosslinked polyethylene in a test tube containing I00 cc of xylene stabiwherein R is selected from the group consisting of cylized with 0.! g of phenolic antioxidant, i.e., 4,4 -thiocloalkyl having 5-30 carbon atoms and phenyl', R, is bis(3-methyl-6-tert-butyl-phenol). The operation is selected from the group consisting of hydrogen, alkyl having l-l2 carbon atoms, and phenyl; and R and R together with the carbon atom to which they are bonded may form a cycloaliphatic hydrocarbon ring having -30 carbon atoms; R: and R are each selected from the group consisting of hydrogen, alkyl having l-l2 carbon atoms. and phenyl', and R and R taken together with the two adjacent carbon atoms to which they are respectively bonded may form a cycloaliphatic hydrocarbon ring having 5-25 carbon atoms; and R, and R, are each selected from the group consisting of alkyl having 4-12 carbon atoms. phenylalkyl having 9-18 carbon atoms, cycloaikyl having 5-2l carbon atoms, and phenyl cycloalkyl having 9-25 carbon atoms.

2. The peroxide of claim I, l-phenyl-3,3-di-(ter.- butyl-peroxy)-propenel 3. A process for the preparation of an organic peroxide having the formula:

they are respectively bonded may form a cycloaliphatic hydrocarbon ring having 5-25 carbon atoms; and R and R are each selected from the group consisting of alkyl having 4-12 carbon atoms, phenylalkyl having 9-l8 carbon atoms, cycloalkyl having 5-2l carbon atoms and phenylcycloalkyl having 9-25 carbon atoms, this process comprising reacting a hydroperoxide selected from the group consisting of R OOH and R OOH. wherein R and R are as defined above. with an unsaturated carbonyl compound having the formula:

wherein R., R R R are as defined above dissolved in a solvent in the presence of a sulfonic acid catalyst at a temperature between about 30 and +C. the molar ratio of said carbonyl compound to said hydroperoxide being between about l:2 and I: I0.

4. The peroxide of claim 1 wherein R and R are tertiary alkyl.

5. The peroxide of claim 4 wherein R and R are selected from the group consisting of tertiary butyl, tertiary amyl. and cumyl.

6. The process of claim 3 wherein the said molar ratio is between about l:2.5 and 1:5.

7. The process of claim 3 wherein said reaction temperature is between about -l0 and 50C.

8. The process of claim 3 wherein said sulfonic acid catalyst is p-toluene sulfonic acid.

@32 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent NO- Dated July 22,

Inventor) Egeo SACRINI and Claudio CAVALOTTI It is certified that error appears in the above-identified patent apd that said Letters Patent are hereby corrected as shown below:

Title page, left side, under "Foreign Application Priority Data": "April 11, 1970 Italy 20222/69" should read July 29', 1969 Italy 20222-A/69 Column 1, line 57$ "cyloaliphatic" should read cycloaliphatic Column 3, lines 32-33: "perferably" should read preferably Column 4, line 48: "1,427.," should read 1.427,,

Columns 7-8, Table 2, second formula:

" OOC(CH 3 CH=CH-CH should read:

0 \OOC(CH3)3 OOC(CH3)3 L CH=CH-CH 0 O0C(CH3) 3 Signcd and Scaled this fourth Day 0; November {975 [SEAL] Arrest:

aura c. uAsoN cmnsmu. [mm

Auem'ng Officer Commissioner nl'l'arenn and Trademurkz 

1. AN ORGANIC PEROXIDE HAVING THE FOMULA: R1-C(-R2)=C(-R3)-C(-R4)(-O-O-R5)-O-O-R6 WHEREIN R1 IS SELECTED FROM THE GROUP CONSISTING OF CYCLOALKYL HAVING 5-30 CARBON ATOMS AND PHENYL, R2 IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL HAVING 1-12 CARBON ATOMS, AND PHENYL, AND R1 AND R2 TOGETHER WITH THE CARBON ATOM TO WHICH THEY ARE BONDED MAY FORM A CYCLOALIPHATIC HYDROCARBON RING HAVING 5-30 CARBON ATOMS, R3 AND R4 ARE EACH SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL HAVING 1-12 CARBON ATOMS, AND PHENYL, AND R3 AND R4 TAKEN TOGETHER WITH THE TWO ADJACENT CARBON ATOMS TO WHICH THEY ARE RESPCTIVELY BONDED MAY FORM A CYCLOALIPHATIC HYDROCARBON RING HAVING 5-25 CARBON TOMS, AND R5 AND R6 ARE EACH ELECTED FROM THE GROUP CONSISTING OF ALKYL HAVING 4-12 CARBON ATOMS, PHENYLALKYL HAVING 9-18 CARBON ATOMS, CYCLOALKYL HAVING 5-21 CARBON TOMS, AND PHENYL CYCLOALKYL HAVING 9-25 CARBON ATOMS.
 2. The peroxide of claim 1, 1-phenyl-3,3-di-(ter.-butyl-peroxy)-propene-1.
 3. A PROCESS FOR THE PREPARATION OF AN ORGANIC PEROXIDE HAVING THE FORMULA: R1-C(-R2)=C(-R3)-C(-R4)(-O-O-R5)-O-O-R6 WHEREIN R1 IS SELECTED FROM THE GROUP CONSISTING OF CYCLOALKYL HAVING 5-30 CARBON ATOMS AND PHENYL, R2 IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL HAVING 1-12 CARBON ATOMS, AND PHENYL, AND R1 AND R2 TOHETHER WITH THE CARBON ATOM TO WHICH THEY ARE BONDED MAY FORM A CYCLOALIPHATIC HYDROCARBON RING HAVING 5-30 CARBON ATOMS, R3 AND R4 ARE EACH SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL HAVING 1-12 CARBON TOMS, AND PHENYL, AND R3 AND R4 TAKEN TOGETHER WITH THE TWO ADJACENT CARBON ATOMS TO WHICH THEY ARE RESPCTIVELY BONDED MAY FORM A CYCLOALIPHATIC HYDROCARBON RING HAVING 5-25 CARBON ATOMS, AND R5 AND R6 ARE EACH SELECTED FROM THE GROUP CONSISTING OF ALKYL HAVING 4-12 CARBON ATOMS, PHENYLALKYL HAVING 9-18 CARBON ATOMS, CYCLOALKYL HAVING 5-21 CARBON TOMS AND PHENYLCYCLOALKYL HAVING 9-25 CARBON ATOMS, THIS PROCESS COMPRISING REACTING A HYDRROPEROXIDE SELECTED FROM THE GROUP CONSISTING OF R5OOH AND R6OOH, WHEREIN R5 AND R6 ARE AS DEFINED ABOVE, WITH AN UNSATURATED CARBONYL COMPOUND HAVING THE FORMULA: R1-C(-R2)=C(-R3)-C(-R4)=O WHEREIN R1, R2, R3, R4 ARE AS DEFINED ABOVE DISSOLVED IN SOLVENT IN THE PRESENT OF A SULFONIC ACID CATALYST AT A TEMPERATURE BETWEEN ABOUT -30* AND +80*C, THE MOLAR RATIO OF SAID CARBONYL COMPOUND TO SAID HYDROPEROXIDE BEING BETWEEN ABOUT 1:2 AND 1:10.
 4. The peroxide of claim 1 wherein R5 and R6 are tertiary alkyl.
 5. The peroxide of claim 4 wherein R5 and R6 are selected from the group consisting of tertiary butyl, tertiary amyl, and cumyl.
 6. The process of claim 3 wherein the said molar ratio is between about 1:2.5 and 1:5.
 7. The process of claim 3 wherein said reaction temperature is between about -10* and 50*C.
 8. The process of claim 3 wherein said sulfonic acid catalyst is p-toluene sulfonic acid. 